Azo dyestuffs



atented Oct. 31, 1944 2,361,642 AZO nrns'rnrrs EmilEduard Misslin and Rudolf Thomann, Basel, Switzerland, assignors to the firm of Society of Chemical Industry in Basle, Basel, Switzerland No Drawing. Application February 9, 1938, Serial r 4 Claims.

' Processes are known for introducing aryl residues having external amino-groups into dyestuffs and their intermediate products in order to change such compounds into products that may be diazotized on the fibre and developed with suitable coupling components to fast dyestufis (compare Colour Index Nos. 324 and 324a).

This invention is based on the observation that in respect especially of the properties and in particular strength of the dyestuffs produced by di azotization and development on the fibre by suitable coupling components and also their intermediate products the results produced are improved by introducing by'known methods into an intermediate product or azo-dyestufi' containing an amino-group an externally bound aryl residue which contains two amino-groups, at least one of which contains as a substituent an acyl res due having at least one amino-group capable of being diazotized.

The new products are thus characterized by the presence of the atomic grouping in which X is hydrogen or an acyl-group, itself carrying an amino-group capable of being diazotized, and Y is an acyl-group which also carries an amino-group capable of being diazotized.

It is also possible to introduce the atomic grouping defined above by first reducing a dinitrated aromatic acid, for instance dinitrobenzene-carboxylic or sulfo-nic acid to the corresponding nitro-amino or diamino acid, condensing the latter with one or 2 mols of an acylating agent which contains a group convertible to an amino-group capable of bein diazotized, then converting the condensation product into its corresponding acid chloride, condensing this latter with a su'table parent material containing an amino-group and finally converting into the amino-group, the group so convertible. These products, which are characterized by the pres ence of the above atomic grouping, may then be developed as such to dyestuffs on the fiber or, in case they have positions suitable for coupling, as is the case, for example, if the parent material is an amino-hydroxynaphthalene derivative, converted into dyestufis by means of suitable diazo-compounds, which dyestuffs still have the characteristic atomic grouping, so that they may be further developed on the fibre.

Among parent materials which come into ques tion for introducing into the intermediate prod- In Switzerland February 10,

uct the external group having two nitro-groups there may be named dinitrobenzoylchloride, dinitrobenzenesulfochloride, dinitrophenoxyacetic acid. chloride, dinitrobenzaldehycle or the like. Among acylating agents which come into question for introducing the acyl-groups indicated by X and Y which contain a group capable of being diazotized may be named meta-nitrobenzoylchloride, para-nitrobenzoylchloride, para-nitrophenoxyacetic acid chloride, meta-nitrobenzenesulfochloride or the like. If in such products the nitro-group is exchanged for an easily eliminated acidylamino-group the latter can be saponified.

after the condensation is complete.

As suitable intermediate products containing at least one amino-group which condense with dini trobenzoylchloride or its above-named equivalents and may then be further worked-up may be named the simple amines of the benzene series and their substitution products, for example aniline, its ortho-, para, or meta-sulfonic acids, naphthylamines and their sulfonic acids, aminohydroxynaphthalene-sulfonic acids, particularly 1-amino-8-hydroxynaphthalene-3 6- or -4 6-disulfonic acid and 2-amino-5-hydroxynaphthalene-l-sulfom'c acid, particularly 1:7-disulfonic acid, also diamines such as ortho-, metaor paraphenylenediamine, 1:8-naphthylenediamine or its sulfonic acid, 1 :2-diamino-5-hydroxynaphthalene-7-su1fonic acid; also products which belong to other series, for instance 4:4'-diaminostilbene- 2:2-disulfonic acid, dehydrothiotoluidin-monoand -di-sulfonic acid, dehydrothioxylidinedisulfonic acid, sulfonic acids of the primuline base.

The new products, whether they are dyestufis or-intermediate products, are characterized in the most part by a pronounced afiinity for vegetable fibres so that they are adsorbed by these from neutral or feebly alkaline baths and may then be converted on-the fibre by diazotization and development with coupling components into dyestuffs. In the case of intermediate products this is especially so if in the processes indicated in the introduction there are selected as parent materials thiazole-sul fonic ac ds, such as dehydrothiotoluidine-disulfonic acids or diaminostilbenedisulfonic acid.

The dyestufis obtainable by the invention are characterized by an abundance of externally diazotizable amino-groups without, however, having too high molecular weight. They are thus characterized by the high coloring strength of the dyeings diazotized on the fibre.

The following examples illustrate the inven tion, the parts being by weight:

Ezcmple 1 A solution of 453 parts of 1 -(3:5-diamino)- benzoylamino-8-hydroxynaphthalene 3:6- disulfonic acid obtainable by condensing 3:5-dinitrobenzoylchloride with 1: 8-aminonaphthol-3: 6-disulfonic acid and subsequent reduction is caused to react with about 370 parts of para-nitrobenzoylchloride and about 120 parts of calcium carbonate at 80-100 C. until no free amino-group is to be detected. The sparingly soluble condensation product is isolated, reduced in known manner by means of iron and acetic acid, made alkaline with sodium carbonate, filtered from the iron and iron salts, and the product is finally precipitated by acidifying the feebly alkaline solution or salting out the sodium salt.

The 1-[3:5'-di-(4":4"-diamino)benzoylam ino] benzoylamino-8-hydroxynaphthalene-3 6- disulfonic acid of the formula thus obtained is, when dry, a grey-white powder HO NH.CO

freely soluble in alkalis and is capable of being tetrazotized in mineral acid suspension and being is used, by condensation in each case with 2 mols of metaor para-nitrobenzoylchloride and reduction similar compounds are produced, for example compounds of the formula nmooO-mn Furthermore, similar compounds are obtained if one of the amino-hydroxynaphthalenesulfonic acids used here as parent material is first condensed with 2:4-dinitrophenoxyacetic acid chloride, then reduced, condensed with 2 mols of one of the aforesaid nitrobenzoylchlorides, and finally coupled easily in alkaline solution with diazocompounds. V

The substitution of para-nitrobenzoylchloride by meta-nitrobenzoylchloride leads to a product. of the formula 1 r- NECOO on Nl'LCO I r m,

- sumo-O SOIH HOaB

The reaction is similar whenfor example 215-- aminonaphthol-l:l-disulfonic acid or 2:5-aminonaphthol-l-sulfonic acid is used instead of 1 8-aminonaphthol-3 fi-disulfonic acid.

It instead of 1-(3':5'-diamino)benzoylamino- 8-hydroxynaphthalene-3:6-disulfonic acid the 1-01 methyl 3':5' diamino)benzen,esulfonylamino-8-hydroxynaphthalene-3 G-disulfonic acid fonylamino-5 hydroxynaphthalene 7 sulfonic acid of the formula .uble in alkalis.

reduced. Such a compound has for example the following formula Hots -NH.C oomoQrmooO-msa QNH:

SOaH 000E ll NH.CO O

NEGOQ NH:

Example 2 403 parts of 2-(3'-amino'-5-nitro) benzylamino- 5-hydroxynaphthalene-Y-sulfonic acid are dissolved in dilute sodium carbonate solution so as to produce a neutral solution and condensed in the presence of chalk with parts of paranitrobenzoylchloride at 70-95 C. with vigorous stirring. After reduction with iron and dilute acetic acid the iron salts are precipitated by means of sodium carbonate, filtered and the filtrate acidified to precipitate the 2[3-(4"- amino) benzoylamino 5 aminolbenzoylamino 5-hydroxynaphthalene-7-su1fonic acid in the form of a colorless sparingly soluble precipitate which when dry is a light grey powder freely sol- The new compound has the following constitution:

accuses I H035 NH.oo-C NH,

NH.C

is obtained, whereas the exchange of the paranitrobenzoylchloride for the para-nitrophenoxy acetic acid chloride leads to a compound of the From Z-amino-E-hydroxynaphthalene 8 sulfonic acid, i-am.ino-8-hydro1cynaphthalene-4=-sulfonic acid, l-(i-Y-ainino) -phenyl--pyrazolone-3- carboxylic acid there are obtained in similar mannor the products of the formulas:

1 NILCOONH;

IFIH:

:1: t 1 Nirco coon DHLCOGNH:

Example 3 The carboxylic'acid chloride compound obtained by the action of phosphorus pentachloride on the 3- (4'-nitro) benzoyl-amino 5 nitrobenzoic acid (produced by condensation of 1 mol para-nitrobenzoyl chloride with 1 mol 3:5-nitroaminobenzoic acid according to known methods) is con densed in molecular proportion in the presence of chalk for maintaining the reaction neutral with 2-amino-5-hydr0xynaphthalene-7-sulfonic acid in an aqueous solution at about 100 C. and while lute acetic acid. After working up in the usual manner there is obtained the new acid described in Example 2, first paragraph.

Example 4 7 One gram mol. of the carboxylic acid chloride compound described in Example 3 is allowed to act in the presence of chalk and while well stirring on a neutral aqueous solution of one gram mol. 1-(3'-amino-5-nitro)benzoylamino 8 hydroxynaphthalene-ii:G-disulfonic acid until the aroylation of the amide group is complete. After reducing with iron and dilute acetic acid and working up according to known methods, the new compound of the formula r m surco Nu,

NILCO 11 ms S01 xrrc oOxm is obtained as a nearly colorless powder which is easily soluble in dilute alkalies and can be hexazotized, and which couples easily in alkaline solution with diazo compounds.

Example 5 I A neutral solution of 370 parts of dvy-diaminostilbene-2:2'-disulfonic acid is mixed with an excess of chalk and then treated, while Vigorously stirring, at -100 0. with 3-acetaminofi-nitrobenzoylchloride until no free amino-group is found to remain. The mixture is then reduced with iron and dilute formic acid and from the solution freed from the iron salt the 4:4K-di-(3- acetamino-5-amino)benzoylaminostilbene 2:2 disulionic acid is isolated by acidification.

This compound is dissolved to a neutral solution in water, and in presence of enough chalk to maintain neutrality during the reaction is treated with about 370 parts of para-nitrobenzoylchloride at Bil- C. until no more free aminogroup can be detected. Reduction in the usual manner follows and the acetamino-group is con verted into the amino-group by saponification with caustic alkali in known manner.

The new compound, which probably has the formula soar-r u'HnOO-Nm I; t y a I I NH: N111 l I: CHGNILCOO NELC 005K115 is, when dry, a yellowish white powder soluble in alkalis to a feebly yellow solution.

When cotton is treated, in the manner adopted for dyeing with substantive dyestufis, with a. solution alkaline with sodium carbmate of the new well stirring and then reduced with iron and di 75 compound it remains nearly colorless and on treatment with acid and nitrite acquires the yellow-orange color of the sparingly soluble octazocompound; by then coupling with alkaline fl-na'phthol solution there is produced a brilliant intense rd-orange fast to washing or with 3-11 droxy-naphthoic acid a deep red or with l-phenyl-3-methyl-5-pyrazolone an intense yellow.

, Example 6 The 2:4 diaminophenyl-l:Z-naphthimidazole- 5-hydroxy-7-sulfonic acid of the probable formula which may be made by usual method from 340 parts of 1:2 diaminonaphthalene-.5:7-disulfonic acid and 196 parts of 2:4-dinitrobenzaldehyde is treated at boiling temperature in the presence of chalk with at least 444 parts of 3-nitrobenzenesulfochloride until free amino-groups ccan no longer be detected. The sparingly soluble condensation product is precipitated and is reduced by means of iron and dilute acetic acid; the solution made alkaline is filtered, and acidified to I precipitate the reduced condensation product.

The new condensation product has the formula Example 7 400 parts of dehydrothiotoluidinedisulfonic 1 acid are caused to react in neutral solution at about 80 C. with 262 parts of 2:4-dinitrophenoxyacetic acid chloride, care being taken simultaneously to neutralize with sodium carbonate the hydrochloric acid produced. By reduction with iron and dilute acetic acid a compound having the probable formula 303K s 03H is produced in the usual manner.

When this compound is neutral solution and in presence of a neutralizing agent such as CaCOa, MgCOs or NazCOs is allowed to react at 80-100 Example 8 93 parts of aniline diazotized in the usual man 1181' are coupled with 691 parts of the intermediate product described in the first or second para .graph of Example 1 at 0-5" C. in. presence oi sodium carbonate. The dyestufi thus produced of the formula NH.COC NH:

NH.C 00cm,

HO NELCO HOaS 50:11

is salted out with common salt at 80 C. and filtered hot. When dry, it is a red powder; it dyes cotton very pure bluish red which when diazotized and developed with p-naphthol'becomes a very intense brilliant red fast to washing.

Similar dyestuffs are obtained when instead of aniline, ortho-toluidine, meta-xylidine, ortho anisidine, para-chloraniline, p-naphthylamine or the like is used.

The use as coupling components of compounds such as NH.CO

HO NH.O O NHz Nam-ONE,

NHCOONH,

Boss

HO ITIELCO C. with 370 parts of 3-nitrobenzoylchloride until the diazo reaction disappears and after filtration the sparingly soluble condensation product thus produced is reduced with iron and dilute acetic I acid in the usual manner and the product worked up there is obtained a compound of the probable formula leadsvto similar products.

A yellow dyestuif, which when further diazotized on the fiber and developed with 1-pheny1-3- methyl-5-pyrazolon'e is'intensely yellow, is obtained by diazotizing 173 parts of sulfanilic acid and coupling with-59l parts of the compound of NmooomoQNmoo NH in dilute acetic acid and isolating the product by salting out from a solution alkaline with sodium and couplingwith 472 parts of the compound last carbonate. The dyestufi has the formula. named in the fourth paragraph of Example 2 in g N'H.CO

' NHJJO-ONH:

Example 9 dilute acetic acid solution and then salting out 12.1 parts of meta-xylidine are diazotized in from a solution alkaline with sodium carbonate. known manner and at -10 C. the solution is It has the formula allowed to flow into a solution alkaline with Example 10 sodium carbonate of 52 parts of the intermediate 2.77} parts of pars"aminoazobenzenesulmmc Product 0f the first Paragraph 0f Example acid are diazotized at 540 0. and the solution is The Operation is complete witihm minutes 30 added to an ammoniacal solution of 492. parts of While stirring well. After standmgior 1 110111 at t intermediate product of th fi t paragraph the said temperature the mass is further stirred of Example After sometime so much Gammon and filtered with suction. The solid matter is n; is added t t mm of t dyestuff t t q tly w shed w h a little ld w rthere is produced a. common salt solution of 15 This dyestufi of the formula per cent. strength. This is heated. to 58 Q.

is a red brown powder when dry. It dyes cotton filtered. The residue is again stirred into a solupure bluish red. By diazotization on the fibre tion of common salt alkaline with sodium carand development with p-naphthol there is ob- I bonate and of 17 1%., the whole is boiled and tained a. brilliant red of very good fastness to filtered with suction. The dyestufi of the forwashing. mule. Y

NrLc oc GONE:

Instead of meta-xylidine there may be used thus obtained is, when dry, 9. pure dark bronze aniline, ortho-toluidine ortho-anisidine, paracolored powder. It dyes cotton bluish red. By

chloraniline, fi-naphthylamine or the like. Val- 60 diazotizing the dyeing and developing with puable similar dyestuffs are also obtained when naphthol there is produced an intense brilliant other azo-components than those named above red which is very fast to washing.

are used, for example the product obtained from By diazotizing the para-toluene-sulfoester of 2-(3'-amino-5'-nitro) benzoylamino -5- hydroxy- 1-amino-8-hydroxynaphthalene 3:6 disulfonic naphthalene-'T-sulfonic acid by condensation with as acid coupling with 5 hyd1=qumned1 1 mo! meta-nitrobenzoylchloride and subsequent ethyl ether and diazofizmg the intermediate reduction; or the product obtained from 2-(3':5'- sum in known manner there is obtained a i ammo) bemylammo' 5 'hydroxynaphtha'lene' component which when added in equivalent pro- 7-sulionic acid by condensation with 2 mols. of

13011101]. to a. solution alkaline with sodium carilrixeggorlilitrobenzoyl chloride and subsequent re 7o te of einte te p not of tor A yellow d t fi which when further diaz second paragraph of Example 1 at 0 5 C. couples tized on the fibre'and developed withl-phenyl-3- to 101m 8 blue (1188mm when this y 15 methyl-S-pyrazolone is intensely yellow, is obitem by the usual method in alkaline solution tained by 1'13 parts of sulfanilic acid, from the para-toluenesulfo-residue and isolated there is obtained a dark violet dyestuff powder of the formula OCzHa H? HOaS \SOBH 1103s -SOaH This disazo-dyestufi dyes cotton blue; by diazotizingand developing with 1-phenyl-3-methyl- 5-pyrazolone an intense green is produced.

If the diazo-component obtained from 2-diazonaphthalene-5-sulfonic acid by diazotizing and coupling with 1-amino-2'-methoxynaphthalene 6 sulfonic acid and further diazotizing is added to an equivalent proportion of an ammoniacal solution containingpyridine'of the in- OClHs SOaH termediate product of the first paragraph of Ex ample 2 at 0-5 0.; there is produced a blue dyestuff which after expulsion of the pyridine is directly filtered and dried. The dyestuii dyes cotton directly blue; when diazotized on the fibre and developed with 1-phenyl-3-methy1-5pyrazolone it yields an intense green.

A further green dyestufi may be obtained by coupling the intermediate product of the first paragraph of Example 2 in the presence of pyridine with the diazotized mon'oazo-dyestuff from 1 diazo 2:5-dich1orobenzene-4-su1fonic acid and 1-amino-2-methoxynaphthalene-6- sulfonic' acid. This new dyestufi of the formula I Hogs N=NQ N=N.

and developing with -1-phenyl-3-r nethyl-5-pyrazolone the blue-green dyeing becomes a brilliant intense green fast to washing.

Similar dyestuffs are obtained if in this example the end component is exchanged for an- 05 of the formula HOaS other amino-naphthol derivative referred to in Example 1 or 2.

Example 11 A green trisazo-dyestufi may be obtained by coupling the intermediate product of the first paragraph of Example 2 in presence of pyridine with the diazotized disazo-dyestufi from diazotized para-aminoazobenzenesulfonic I acid and 1 amino 2 methoxynaphthalene-fi-sulfonic acid. The new dyestufi of the formula 1 Hots NH.O 0Q

'or second paragraphv of Example 1 in a solution alkaline with sodium carbonate with the diazotizecl disazo-dyestuff obtainable by coupling the para-toluene-sulfonic acid ester of 1-diaz'o-8-hydroxynaphthalene-3:G-disulfonic acid with 1- ami-no-Z:5-hydroquinone-diethyl ether and fur I NIELCOQ NIELC DONE:

dyescottonblue green; by diazotizing on thefi bre go'ther diazotizing this monoazo-dyestufi and coupling with a mixture of l-ax'nino-naphthalene-G- and -7-sulfonic acids. By eliminating the paratoluene'sulfo-residue in alkaline solution and isolating the 'dyestuff there is obtained a dyestufi NILC OONHQ no Nmco I V I 4 no N=NQN=N N=N N'ELOOONH: om. riots on: I

a BOaH ample there is substituted for the final components another aminonaphth'ol derivative name in Example 1 or 2.

Example 12 immediately introduced into a developing bath containing 0.4 per cent of 1-phenyl-3-methyl-5- pyrazolone and 0.2 per cent of sodium carbonate.

There is produced an intense pure green dyeing.

What we claim is: 1. The azo-dyestufls of the general formula in which R stands for an aromatic radical of the benzene series, R2 stands for the radical of a coupling component containing at least one amino group, :1: stands for a linking group which has been formed by the action of a member of the group consisting of COOH and SO3H linked to the benzene nucleus, on an amino group of the coupling component corresponding to the symbol R2, in which t stands for a member of the group consisting of the NHz group and an NH: group acidylated by an acyl radical containing a diazotizable amino group, and 1: stands for a NH: group acidylated by an acyl radical containing a diazotizable amino group, which products are more or less dark powders which dissolve in water to yellow, to orange, to red, to violet, to blue and to green solutions which dye the fiber similar tints and which are diazotizable on the fiber and capable of being developed with p-naphthol and 1-phenyl-3-methylr5-pyrazolone.

2. The azo-dyestufis of the general formula fl' r t in which the naphthalene nucleus carries at least one sulfonic acid group, one 3 stands for a OH- group and the other y stands for a hydrogen atom, one 2 stands for a member of the group consisting of a SOsH group and a hydrdogen atom and the other 2 stands for a -N=N-R group wherein R means an aromatic radical of the benzene series and wherein the --N=NR group stands in ortho-position to the OH-group, in which a: stands for a linking group which has been formed by the action of a member of the group consisting of COOH and SOsH linked to the benzene nucleus, on amino groups linked to the naphthalene nucleus, in which t stands for a member of the group consisting of the amino group and an amino group acidylated by an acyl radical containing a diazotizable amino group, and 1; stands for an amino group acidylated by an acyl radical containing a diazotizable amino group, which products are more or less dark powders dissolving in water to red, to violet, to blue and to green solutions and dyeing the fiber similar tints.

3. An azo dyestufi of the formula NH N H: the benzene wherein R is an aromatic nucleus of series.

4. An azo dyestufi of the formula:

- EMIL EDUARD MISSLIN.

RUDOLF THOMANN. 

